Stable lead alkyl compositions and a method for preparing the same



Patented Nov. 24, 1953 STABLE LEAD ALKYL COMPOSITIONS AND A METHOD FOR PREPARING THE SAME George Calingaert, Geneva, N. Y., assignor to Ethyl Corporation, New York, N. "id, a corporation of Delaware No Drawing.

Application March 18, 1952,

l Serial No. 277,283 17 Claims. (01. zoo-437) This invention relates to alkyllead compositions which are stable at temperatures above 160 C. It also relates to methods for inhibiting the thermal decomposition of alkyllead compounds when subjected to temperatures above 100 0., at which temperature thermal decomposition becomes appreciable.

Generally my invention contemplates inhibiting the thermal decomposition of alkyllead compounds in which at least one valence of the lead is satisfied by an alkyl radical.

More specifically, my invention is concerned with an improved process for separating alkyllead compounds from the reaction products accompanying their synthesis. It is also applicable to a method for inhibiting thermal decomposition of an alkyllead product during its formation or during any step of the process including blending with other products in making the commercial antilznock fluid. It is applicable to minimiz-- ing the possibility of thermal decomposition during storage or transportation of an alkyllead product. It is especially applicable to preventing thermal decomposition of mixtures containing a high concentration of an alkyllead compound. The likelihood of thermal decomposition is more of a problem at high concentrations of lead aliryls, i. e., compositions above 80% by Weight.

As is Well known, tetraalkyllead antiknock compounds generally are produced by reacting an alloy of lead and a dissimilar metal usually sodium, with an alkylating agent such as alkyl hali usually an alkyl chloride. The tetralead compound is produced thereby in admixture with Various reaction lay-products from which it be separated. Separation is accomplished ordinarily by steam or vacuum distillation with subsequent purification of the tetraallryllead distillate. Due to the toxic and ups; ole nature or" tetraallzyllead antiknock compounds, the foregoing process is subject to many dirliculties.

In the manufacturing operations of alkyllead compounds meticulous temperature control and exact safety measures are of paramount importance. The rate of decomposition of the alkylcompound increases rapidly with small rises in telnerature above the temperature where thermal decomposition becomes appreciable. For example, decomposition of tetraethyllead occurs at the rate of approximately 2 per cent per hour at a temperature of 100 6., which is the custernary temperature used in separating tetraethyllead from the reaction products accompanying its synthesis. At temperatures above 100 C.

the decomposition rate increases logarithmically so that a point is soon reached Where external heat is no longer required and decomposition becomes self-propagating.

Generally the manuiacture of a tetraalkyllead, for example, tetraethyllead, involves the following steps: reaction, separation from reaction products, purification and blending. The reaction and separation steps of the alkyllead process which are conducted at or near decomposition temperatures require extensive and careful precautionary measures in order to minimize, and to provide for, excessive decomposition due to sudden and unavoidable increases in temperature.

Such likelihood ofexcessive decomposition is present also during blending, handling, storage and transportation. Prior to diluting the alkyllead concentrate with scavengers, gasoline or other materials, the alkyllead compound remains a concentrate and the problem of excessive thermal decomposition exists, even though the temperature is maintained normally well below that of decomposition. For example, in the purification step wherein the tetraethyllead concentrate is washed and blown with air at atmospheric temperature to remove impurities, a sudden increase in temperature may occur due to the oxidation of triethylbismuth which is present as an impurity. Also pumps used in handling tetraethyllead occasionally freeze and the friction developed may cause a local overheating to a temperature above the temperature of decomposition of the tetraethyllead. Faulty wiring, leaks onto steam pipes, and other accidental causes also may produce local overheating with resulting dangerous decomposition.

Therefore, it is an object of my invention to stabilize alkyllead compounds in which at least one valence of the lead is satisfied an alkyl radical, against thermal decomposition during one or more of the following operations: manufacture, purification, blending, transportation and storage.

I accomplish this object by incorporating with alkyllead compounds a relatively small quantity of a material which I have found has the property of inhibiting and substantially preventing their decomposition when subjected to elevated temperature conditions. Furthermore, I accomplish this object by conducting one or more steps of the inanufacturing process for the alkyllead compound, particularly the separation step, the presence of such a material. The materials which I have found to possess this property are referred to hereinafter as thermal stabilizers.

These thermal stabilizers are various different types of compounds. Fused-ring hydrocarbons and halogenated derivatives of these hydrocarbons are particularly effective, as well as up saturated compounds having boiling points at least as high as 1 C. at atmospheric pressure. Of these unsaturated compounds best results are obtained when they are olefin hydrocarbons including aryl-substituted olefins. The substitution of halogens for part or all of the hydrogen atoms in such unsaturated compounds also gives highly effective thermal stabilizers.

Aliphatic nitro compounds, as well as aliphatic nitrates and aliphatic nitrites, form another very efiective class of thermal stabilizers according to the present invention.

Compounds that have a boiling point below 1 C. at atmospheric pressure are of no appreciable value as thermal stabilizers. It appears that such compounds in addition to their low effectiveness are substantially insoluble in the alkyllead com pounds to be stabilized, and can accordingly not be mixed with these compounds in the desired proportions.

I have found that my thermal stabilizers when used in amounts varying from 0.01 to 5.0 per cent by weight of the lead alkyl product are effective in substantially retarding or preventing thermal decomposition at temperatures above 100 C. for an extended period of time, e. g., ten to twenty hours at 130 C., which period is sufficient for all contemplated commercial applications.

A representative group of my thermal stabilizers are the following: crotonaldehyde, allo-- ocimene, butadiene, di-amylene, dipentene, heptene, trimethylethylene, triphenylchlormethane, styrene, divinylbenzene, cyclohexene, dicyclopentadiene, allyl iodide, chloroprene, hexachloropropylene, ethynylcyclohexanol, glyceryl monostearate, glycol dilaurate, tiglic alcohol, alloxan, azobenzene, 2,2-azonaphthalene, 4-benzeneazol-naphthylamine, n-butyl nitrate, n-butyl nitrite, nitroethane, nitromethane, 2-nitro-2-methyh1- propanol, p-nitrobenzoic acid, p-nitroaniline, allyl isothiocyanate, anthracene, chrysene, naphthalene, alpha-methyl naphthalene, alpha-bromonaphthalene, chloronaphthalene, alpha-naphthol, beta-naphthol, naphthoresorcinol, betanaphthoquinoline, tetrahydronaphthalene, indene, stearyl iodide, styrene dibromide, phloroglucinol, di-isobutylene, tetramethylethylene, tribromoethylene, oleic acid, cinnamic acid dibromide, maleic anhydride, phthalic anhydride, aluminum oleate, ethyl thiocyanate, hexachloroethane, 2-

amino 2 methyl l propanol, 2 ethyl 1,3

hexanediol, iodoform, furfural, chlorophyll, lecithin, pyrophosphaditic acid, semi-carbazide hydrochloride, stilbene, methyl styrene, o-bromostyrene, p-chlorostyrene, o-ethylstyrene, o-chlorostyrene, aconitic acid, ethylene dibromide, resorcinol, 2,4,6-tri (dimethylaminomethyl) phenol, 2-methyl-2,4-pentanediol, ethylene bromohydrin, alpha-terpineol, acetyl aminothiophene, ethanolamine, p-p'-diaminodiphenylmethane, acridine, furfuryl alcohol, furfuryl amine, 8-hydroxyquinaldine, lepidine. Of these compounds the butadiene has the lowest boiling point, its boiling-point being about 1 C. at atmospheric pressure.

To illustrate the effectiveness of the present invention, direct comparisons were made between the decomposition rates of unstabilized and stabilized tetraethyllead. A thermostatically controlled hot oil bath was fitted with a stirrer, thermometer, and a holder for a small reaction tube. A 100 cc. gas buret beside the bath, and equipped with a water-containing levelling bottle, was connected by means of rubber tubing with the reaction tube after the desired sample was introduced into this tube. After the bath was brought to a steady temperature of 160 C., the sample-containing tube was quickly introduced and clamped with the levelling bottle adjusted to hold the gas buret in place at a zero reading. As the sample decomposed under the influence of the bath temperature, readings were taken over various periods of the amount of gases thus liberated, as indicated by the gas buret.

With pure tetraethyllead used in one milliliter amounts, 10 cc. of gas was liberated in one minute, and 100 cc. of gas in about six minutes. However, if to the same amount of tetraethyllead there is previously added 2% by weight of oleic acid, p-nitrobenzoic acid or semi-carbazide hydrochloride, at the end of 100 minutes only about six cc. of liberated gas was shown. When 2% chlorophyll is used instead of the other stahilizers, even less gas is liberated, The other stabilizers listed above showed about the same degree of efiectiveness.

The liberation of gas is a very good index of the alkyllead decomposition. The principal decomposition products are metallic lead and hydrocarbon gas. When the decomposition becomes selfpropagating, the rate of gas liberation changes from a gradual one to one that becomes very rapid. With the above stabilizers tested at 160 (3., there was no serious rise in gas liberation rate. Normally, however, the decomposition of unstaloilized tetraethyllead will become uncontrollable if it is heated to 130 (3., whether this temperature is reached rapidly or slowly, unless it is possible to very rapidly cool it down to about 100 C. or below.

The above described behavior of the listed stabilizers also takes place with other alkyllead compounds such as triethyllead bromide a tetrapropyl lead. In fact these compounds wh stabilized can be boiled and distilled at atmc pheric pressure, something never before possl because they uncontrollably decompose beioc. they can be heated to these temperatures.

My invention is adapted to the stabilization of tetraethyllead and other alkyllead compounds at various stages during synthesis, separation, purification and blending with other materials. For example one of my thermal stabilizers may be added to the reactants from which the allsyllead compound is produced, regardless of the partia ular reaction employed. Preferably it is added prior to the separation step which conducted at a temperature close to the temperature where hazardous run-away decomposition is particular" 1y prevalent. By adding one of my thermal stabili ers to the reaction mixture prior to distillation, the danger arising from unexpected temperature increases is substantially eliminated.

Also my thermal hi p oyed to stabilize the 30 nd both in stor age and in ship g and especially stabilize any allzyllead con-c rate. If elevated temperature conditions are likely to be encountered, the addition or a small mount of thermal stabilizer to the alkyllead cc ound will economically anal satisfactorily elim-..iate most of the hazard involved. While meticulous temperature control and exacting safety measures have been success-- ful in reducing to a minimum the hazards of processing and hand is of tetraethyllead, the use oi safety lieyond that presently enjoyed. Furthermore, waste of the alkyllead product due to decomposition is considerably minimized through the use of my invention.

My invention is useful in stabilizing alkyllead compounds in which at least one valence of the lead is satisfied by an alkyl radical. For example tetraethyllead, tetramethyllead, tetrapropyllead, dimethyldiethyllead, triethylphenyllead and triethyllead bromide can be successfully stabilized against thermal decomposition by incorporating therein a relatively small quantity of one of my stabilizers.

Depending upon the conditions to which said alkyllead compound is subjected or likely to be subjected, the stabilizer can be selected to be stable to oxidation and/ or to be non-polymerizable at the temperature of reaction of the alkyllead compound. It should be non-objectionable as contained in the final product, and if it is desired to distill the stabilized material, the stabilizer should have a vapor pressure within the range or" the alkyllead product. Besides relative effectiveness, generally all the above properties should be taken into account in selecting the best commercial stabilizer for a given alkyllead compound.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope hereof, it is to be understood that the invention is not limited to the specific embodiments hereof, except as defined in the appended claims.

This application is a continuation-in-part of my copending application, Serial Number 64,259, filed December 8, 1948.

What is claimed is:

1. A method of inhibiting the decomposition of an alkyllead compound comprising incorporating therewith a thermal stabilizer selected from the class consisting of alloxan, p-nitrobenzoie acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

2. A method of inhibiting the decomposition of a tetraethyllead concentrate comprising incorporating therewith from 0.01 to 5.0 per cent by Weight or" a thermal stabilizer selected from the class consisting of alloxan, p-nitrobenzoic acid,

oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

3. In a process of producing tetraethyllead by reacting a sodium-lead alloy with ethyl chloride and separating the thus produced tetraethyllead from the reaction mass by steam distillation, the step which comprises conducting said steam distillation in the presence of a thermal stabilizer selected from the class consisting of alloxan, p-nitrobenzoic acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

l. A new composition comprising an alkyllead compound and a thermal stabilizer selected from the class consisting of alloXan, p-nitrobenzoic acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

5. A new composition comprising at least eighty per cent by weight of tetraethyllead and less than five per cent of an organic thermal stabilizer selected from the class consisting of alloxan, p-nitrobenzoic acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

6. The process which comprises distilling an alkyllead compound at atmospheric pressure from a mixture containing said alkyllead compound and a stabilizer selected from the class consisting of alloXa-n, p-nitrobenzoic acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

'Z. In a process for steam distilling an alkyllead compound, the step of incorporating With said compound, before steam distillation, a thermal stabilizer selected from the class consisting of alloxan, p-nitrobenzoic acid, oleic acid, maleic anhydride, aluminum oleate, phthalic anhydride, aconitic acid, chlorophyll, semi-carbazide hydrochloride and cinnamic acid dibromide.

8. The method of claim 1 further defined in that the thermal stabilizer is maleic anhydride.

9. The method of claim 1 further defined in that the thermal stabilizer is phthalic anhydride.

10. The method of claim 1 further defined in that the thermal stabilizer is cinnamic acid dibromide.

11. The method of claim 1 further defined in that the thermal stabilizer is oleic acid.

12. The method of claim 1 further defined in that the thermal stabilizer is p-nitro-benzoic acid.

13. The process of claim 3 further defined in that the thermal stabilizer is maleic anhydride.

14. The process of claim 3 further defined in that the thermal stabilizer is phthalic anhydride.

15. The process of claim 3 further defined in that the thermal stabilizer is cinnamic acid dibromide.

16. The process of claim 3 further defined in that the thermal stabilizer is oleic acid.

17. The process of claim 3 further defined in that the thermal stabilizer is p-nitro-benzoic acid.

GEORGE CALINGAERT.

Name Date Linch Dec. 9, 1947 Number 

1. A METHOD OF INHIBITING THE DECOMPOSITION OF AN ALKYLLEAD COMPOUND COMPRISING INCORPORATING THEREWITH A THERMAL STABILIZER SELECTED FROM THE CLASS CONSISTING OF ALLOXAN, P-NITROBENZOIC ACID, OLEIC ACID, MALEIC ANHYDRIDE, ALUMINUM OLEATE, PHTHALIC ANHYDRIDE, ACONITIC ACID, CHLOROPHYLL, SEMI-CARBAXIDE HYDROCHLORIDE AND CINNAMIC ACID DIBROMIDE. 